Micropillar with Radial Gradient Modulus Enables Robust Adhesion and Friction.

The gradient modulus in beetle setae plays a critical role in allowing it to stand and walk on natural surfaces. Mimicking beetle setae to create a modulus gradient in microscale, especially in the direction of setae radius, can achieve reliable contact and thus strong adhesion. However, it remains highly challenging to achieve modulus gradient along radial directions in setae-like structures. Here, polydimethylsiloxane (PDMS) micropillar with radial gradient modulus, (termed GM), is successfully constructed by making use of the polymerization inhibitor in the photosensitive resin template. GM gains adhesion up to 84 kPa, which is 2.3 and 4.7 times of soft homogeneous micropillars (SH) and hard homogeneous micropillars (HH), respectively. The radial gradient modulus facilitates contact formation on various surfaces and shifts stress concentration from contact perimeter to the center, resulting in adhesion enhancement. Meanwhile, GM achieves strong friction of 8.1 mN, which is 1.2 and 2.6 times of SH and HH, respectively. Moreover, GM possesses high robustness, maintaining strong adhesion and friction after 400 cycles of tests. The work here not only provides a robust structure for strong adhesion and friction, but also establishes a strategy to create modulus gradient at micron-scale.

3D nanofiber scaffolds from 2D electrospun membranes boost cell penetration and positive host response for regenerative medicine.

The ideal tissue engineering scaffold should facilitate rapid cell infiltration and provide an optimal immune microenvironment during interactions with the host. Electrospinning can produce two-dimensional (2D) membranes mimicking the extracellular matrix. However, their dense structure hinders cell penetration, and their thin form restricts scaffold utility. In this study, latticed hydrogels were three-dimensional (3D) printed onto electrospun membranes. This technique allowed for layer-by-layer assembly of the membranes into 3D scaffolds, which maintained their resilience impressively under both dry and wet conditions. We assessed the cellular and host responses of these 3D nanofiber scaffolds by comparing random membranes and mesh-like membranes with three different mesh sizes (250, 500, and 750 µm). It was found that scaffolds with a mesh size of 500 µm were superior for M2 macrophage phenotype polarization, vascularization, and matrix deposition. Furthermore, it was confirmed by subsequent experiments such as RNA sequencing that the mesh-like topology may promote polarization to the M2 phenotype by affecting the PI3K/AKT pathway. In conclusion, our work offers a novel method for transforming 2D nanofiber membranes into 3D scaffolds. This method boasts flexibility, allowing for the use of varied electrospun membranes and hydrogels in terms of structure and composition. It has vast potential in tissue repair and regeneration.

FKBP5 deficiency attenuates calcium oxalate kidney stone formation by suppressing cell-crystal adhesion, apoptosis and macrophage M1 polarization via inhibition of NF-κB signaling.

Surgical crushing of stones alone has not addressed the increasing prevalence of kidney stones. A promising strategy is to tackle the kidney damage and crystal aggregation inherent in kidney stones with the appropriate therapeutic target. FKBP prolyl isomerase 5 (FKBP5) is a potential predictor of kidney injury, but its status in calcium oxalate (CaOx) kidney stones is not clear. This study attempted to elucidate the role and mechanism of FKBP5 in CaOx kidney stones. Lentivirus and adeno-associated virus were used to control FKBP5 expression in a CaOx kidney stone model. Transcriptomic sequencing and immunological assays were used to analyze the mechanism of FKBP5 deficiency in CaOx kidney stones. The results showed that FKBP5 deficiency reduced renal tubular epithelial cells (RTEC) apoptosis and promoted cell proliferation by downregulating BOK expression. It also attenuated cell-crystal adhesion by downregulating the expression of CDH4. In addition, it inhibited M1 polarization and chemotaxis of macrophages by suppressing CXCL10 expression in RTEC. Moreover, the above therapeutic effects were exerted by inhibiting the activation of NF-κB signaling. Finally, in vivo experiments showed that FKBP5 deficiency attenuated stone aggregation and kidney injury in mice. In conclusion, this study reveals that FKBP5 deficiency attenuates cell-crystal adhesion, reduces apoptosis, promotes cell proliferation, and inhibits macrophage M1 polarization and chemotaxis by inhibiting NF-κB signaling. This provides a potential therapeutic target for CaOx kidney stones.

Robust and Elevated Adhesion and Anisotropic Friction in a Bioinspired Bridged Micropillar Array.

Bioinspired structured adhesives have promising applications in the fields of robotics, electronics, medical engineering, and so forth. The strong adhesion and friction as well as the durability of bioinspired hierarchical fibrillar adhesives are essential for their applications, which require fine submicrometer structures to stay stable during repeated use. Here, we develop a bioinspired bridged micropillars array (BP), which realizes a 2.18-fold adhesion and a 2.02-fold friction as compared to that of poly(dimethylsiloxane) (PDMS) original micropillar arrays. The aligned bridges offer BP strong anisotropic friction. The adhesion and friction of BP can be finely regulated by changing the modulus of the bridges. Moreover, BP shows strong adaptability to surface curvature (ranging from 0 to 800 m-1), excellent durability over 500 repeating cycles of attachment/detachment, and self-cleaning ability. This study presents a novel approach for designing robust structured adhesives with strong and anisotropic friction, which may find applications in areas such as climbing robots and cargo transportation.

Wires with Continuous Sabal Leaf-Patterned Micropores Constructed by Freeze Printing for a Wearable Sensor Responsible to Multiple Deformations.

The design of porous structure in wearable sensors is very important for the detection of mechanical signals. However, it remains challenging to construct a porous structure capable of detecting all kinds of mechanical signals. Here, round wire with long-range orientated micropores (RW-LOM) is fabricated by a newly established freeze printing technique and constructed into a wearable sensor by the incorporation of carbon nanotubes and polydimethylsiloxane. The Sabal leaf-like lamellar structure in RW-LOM is realized and can be tuned by the proper coordination of slurry concentration and the printing parameters. The fine structures in RW-LOM allow the wearable sensor to detect compression, stretching, twisting, and bending with a high sensitivity, stability, and broad detecting range. This work not only provides a wearable sensor with high stability and high sensitivity but also establishes a technique to construct porous wires that could find applications in the fields like intelligent industry and healthcare.

Improvement in Mechanical Properties of 3D-Printed PEEK Structure by Nonsolvent Vapor Annealing.

The broad applications of 3D-printed poly-ether-ether-ketone (3D-PEEK) structures are largely hampered by their inadequate mechanical properties that can be improved by post treatments. At present, thermal annealing is generally used to improve the mechanical properties of 3D-PEEK. However, it cannot simultaneously improve strength and ductility. Here, a cost-effective postprocessing method is developed to improve the mechanical properties of 3D-PEEK, based on annealing in nonsolvent vapor at room temperature. The annealing in nonsolvent vapor at room temperature simultaneously improves the strength, ductility, and fracture energy of as-printed 3D-PEEK by 22.6%, 151.3%, and 109.1%, respectively. The improved mechanical properties are attributed to enhanced interfacial bonding, increased crystallinity, decreased pinhole defects, and stress relaxation in the 3D-PEEK. Moreover, the annealing in both polar solvents (such as acetone and chloroform) and nonpolar solvents (such as n-hexane) are demonstrated to be effective for improving the mechanical properties of 3D-PEEK. The nonsolvent vapor-annealed 3D-PEEK can thus have potential applications in the fields of medical implants, automotive, aerospace, and more.

Adhesion Enhancement of Micropillar Array by Combining the Adhesive Design from Gecko and Tree Frog.

It has long been demonstrated the gecko-inspired micropillar array with T-shape tips possesses the best adhesion performance of a given material. The further enhancement of the adhesion performances of T-shape micropillars can offer redundant adhesion to compensate for the inevitable improper contacts. Here, the array of T-shape polydimethylsiloxane (PDMS) micropillars is incorporated with gradient dispersed calcium carbonate nanoparticles in the micropillar stalk, termed as T-shape gradient micropillars (TG), possessing the modulus gradient with stiff tip and soft root. The gradient modulus in TG facilitates the contact formation and regulates the stress at the detaching interface, resulting in a 4.6 times adhesion and 2.4 times friction as compared with the pure PDMS T-shape micropillar arrays. The study here provides a new design strategy for the super-strong structured dry adhesives.

Springtail-Inspired Superamphiphobic Ordered Nanohoodoo Arrays with Quasi-Doubly Reentrant Structures.

The skin of springtails is well-known for being able to repel water and organic liquids using their hexagonally arranged protrusions with reentrant structures. Here, a method to prepare 100 nm-sized nanohoodoo arrays with quasi-doubly reentrant structures over square centimeters through combining the nanosphere lithography and the template-protected selective reactive ion etching technique is demonstrated. The top size of the nanohoodoos, the intra-nanohoodoo distance, and the height of the nanohoodoos can be readily controlled by the plasma-etching time of the polystyrene (PS) spheres, the size of the PS spheres used, and the reactive ion etching time of silicon. The strong structural control capability allows for the study of the relationship between the nanohoodoo structure and the wetting property. Superamphiphobic nanohoodoo arrays with outstanding water/organic liquid repellent properties are finally obtained. The superamphiphobic and liquid repellent properties endow the nanohoodoo arrays with remarkable self-cleaning performance even using hot water droplets, anti-fogging performance, and the surface-enhanced Raman scattering sensitivity improvement by enriching the analyte molecules on the nanohoodoo arrays. Overall, the simple and massive production of the superamphiphobic nanohoodoo structures will push their practical application processes in diverse fields where wettability and liquid repellency need to be carefully engineered.

Switchable Adhesion of Micropillar Adhesive on Rough Surfaces.

Switchable structured adhesion on rough surfaces is highly desired for a wide range of applications. Combing the advantages of gecko seta and creeper root, a switchable fibrillar adhesive composed of polyurethane (PU) as the backing layer and graphene/shape memory polymer (GSMP) as the pillar array is developed. The photothermal effect of graphene (under UV irradiation) changes GSMP micropillars into the viscoelastic state, allowing easy and intimate contact on surfaces with a wide range of roughness. By controlling the phase state of GSMP via UV irradiation during detachment, the GSMP micropillar array can be switched between the robust-adhesion state (UV off) and low-adhesion state (UV on). The state of GSMP micropillars determines the adhesion force capacity and the stress distribution at the detaching interface, and therefore the adhesion performance. The PU-GSMP adhesive achieves large adhesion strength (278 kPa), high switching ratio (29), and fast switching (10 s) at the same time. The results suggest a design principle for bioinspired structured adhesives, especially for reversible adhesion on surfaces with a wide range of roughness.

Continuous Gradient Nanoporous Film Enabled by Delayed Directional Diffusion of Solvent and Selective Swelling.

Nature-inspired porous structures are highly desired in the fields of new materials, sustainable energy, biological and chemical science, and so forth. Here, a new strategy for the fabrication of continuous, gradient nanoporous polystyrene- block-poly(2-vinylpyridine) (PS- b-P2VP) film is established. The continuous nanopore gradient along the direction of film thickness (∼120 µm) is achieved via delayed directional diffusion of dynamic binary solvent of ethanol/water and selective swelling of P2VP domains. Ethanol in binary solvent diffuses into the film from one side to another, which is retarded by the water gate as water is concentrated at the film surface. The delayed diffusion matches the swelling rate of P2VP domains, forming the continuous nanopore gradient normal to the film surface.

Tree frog adhesion biomimetics: opportunities for the development of new, smart adhesives that adhere under wet conditions.

Enlarged adhesive toe pads on the tip of each digit allow tree frogs to climb smooth vertical and overhanging surfaces, and are effective in generating reversible adhesion under both dry and wet conditions. In this review, we discuss the complexities of the structure of tree frog toe pads in relation to their function and review their biomimetic potential. Of particular importance are the (largely) hexagonal epithelial cells surrounded by deep channels that cover the surface of each toe pad and the array of nanopillars on their surface. Fluid secreted by the pads covers the surface of each pad, so the pads adhere by wet adhesion, involving both capillarity and viscosity-dependent forces. The fabrication and testing of toe pad mimics are challenging, but valuable both for testing hypotheses concerning tree frog toe pad function and for developing toe pad mimics. Initial mimics involved the fabrication of hexagonal pillars mimicking the toe pad epithelial structure. More recent ones additionally replicate the nanostructures on their surface. Finally we describe some of the biomimetic applications that have been developed from toe pad mimics, which include both bioinspired adhesives and friction-generating devices. This article is part of the theme issue 'Bioinspired materials and surfaces for green science and technology (part 2)'.

High drug-loading gold nanoclusters for responsive glucose control in type 1 diabetes.

BACKGROUND: Diabetes is one of the biggest medical challenges worldwide. The key to efficiently treat type 1 diabetes is to accurately inject insulin according to the blood glucose levels. In this study, we aimed to develop an intelligent insulin-releasing gold nanocluster system that responds to environmental glucose concentrations. RESULTS: We employed gold nanoclusters (AuNCs) as a novel carrier nanomaterial by taking advantage of their high drug-loading capacity. We prepared AuNCs in the protection of bovine serum albumin, and we decorated AuNCs with 3-aminophenylboronic acid (PBA) as a glucose-responsive factor. Then we grafted insulin onto the surface to obtain the glucose-responsive insulin-releasing system, AuNC-PBA-Ins complex. The AuNC-PBA-Ins complex exhibited high sensitivity to glucose concentration, and rapidly released insulin in high glucose concentration in vitro. In the type 1 diabetic mouse model in vivo, the AuNC-PBA-Ins complex effectively released insulin and regulated blood glucose level in the normoglycemic state for up to 3 days. CONCLUSIONS: We successfully developed a phenylboronic acid-functionalized gold nanocluster system (AuNC-PBA-Ins) for responsive insulin release and glucose regulation in type 1 diabetes. This nanocluster system mimics the function of blood glucose regulation of pancreas in the body and may have potential applications in the theranostics of diabetes.

Green emitting N,S-co-doped carbon dots for sensitive fluorometric determination of Fe(III) and Ag(I) ions, and as a solvatochromic probe.

N,S-co-doped carbon dots (N,S-CDs) were synthesized via a single-step solvothermal process by using sodium lignosulfonate and p-phenylenediamine as carbon/nitrogen/sulfur sources. The N,S-CDs have an average diameter of 2.02 ± 1 nm and display green fluorescence, with excitation/emission peak wavelengths at 380/540 nm for optimal fluorescence. Fluorescence is excitation wavelength-dependent and stable in aqueous salt solutions. The fluorescence of the N,S-CDs is selectively quenched by Fe(III) and Ag(I) ions. These ions can be quantified by fluorometry with a limit of detection of 1.7 µM for Fe(III) ions and 11.6 µM for Ag(I) ions. The N,S-CDs also undergo solvatochromism in that emission is green in water solution but blue in polar organic solvents such as ethanol or N,N-dimethylformamide. The color of fluorescence gradually shifts from green to blue when continuously increasing the fraction of organic solvent in water. Graphical abstract N,S-co-doped carbon dots (N,S-CDs) are synthesized by using sodium lignosulfonate and p-phenylenediamine as C/N/S sources. The N,S-CDs can sensitively detect Fe(III) and Ag(I) ions based on fluorometry, and can be used as a solvatochromic probe.

Advanced SERS Sensor Based on Capillarity-Assisted Preconcentration through Gold Nanoparticle-Decorated Porous Nanorods.

A preconcentrating surface-enhanced Raman scattering (SERS) sensor for the analysis of liquid-soaked tissue, tiny liquid droplets and thin liquid films without the necessity to collect the analyte is reported. The SERS sensor is based on a block-copolymer membrane containing a spongy-continuous pore system. The sensor's upper side is an array of porous nanorods having tips functionalized with Au nanoparticles. Capillarity in combination with directional evaporation drives the analyte solution in contact with the flat yet nanoporous underside of the SERS sensor through the continuous nanopore system toward the nanorod tips where non-volatile components of the analyte solution precipitate at the Au nanoparticles. The nanorod architecture increases the sensor surface in the detection volume and facilitates analyte preconcentration driven by directional solvent evaporation. The model analyte 5,5'-dithiobis(2-nitrobenzoic acid) can be detected in a 1 × 10-3 m solution ≈300 ms after the sensor is brought into contact with the solution. Moreover, a sensitivity of 0.1 ppm for the detection of the dissolved model analyte is achieved.

Quantifying the structural integrity of nanorod arrays.

Arrays of aligned nanorods oriented perpendicular to a support, which are accessible by top-down lithography or by means of shape-defining hard templates, have received increasing interest as sensor components, components for nanophotonics and nanoelectronics, substrates for tissue engineering, surfaces having specific adhesive or antiadhesive properties and as surfaces with customized wettability. Agglomeration of the nanorods deteriorates the performance of components based on nanorod arrays. A comprehensive body of literature deals with mechanical failure mechanisms of nanorods and design criteria for mechanically stable nanorod arrays. However, the structural integrity of nanorod arrays is commonly evaluated only visually and qualitatively. We use real-space analysis of microscopic images to quantify the fraction of condensed nanorods in nanorod arrays. We suggest the number of array elements apparent in the micrographs divided by the number of array elements a defect-free array would contain in the same area, referred to as integrity fraction, as a measure of structural array integrity. Reproducible procedures to determine the imaged number of array elements are introduced. Thus, quantitative comparisons of different nanorod arrays, or of one nanorod array at different stages of its use, are possible. Structural integrities of identical nanorod arrays differing only in the length of the nanorods are exemplarily analysed.

Stick-Slip Friction of PDMS Surfaces for Bioinspired Adhesives.

Friction plays an important role in the adhesion of many climbing organisms, such as the gecko. During the shearing between two surfaces, periodic stick-slip behavior is often observed and may be critical to the adhesion of gecko setae and gecko-inspired adhesives. Here, we investigate the influence of short oligomers and pendent chains on the stick-slip friction of polydimethylsiloxane (PDMS), a commonly used material for bioinspired adhesives. Three different stick-slip patterns were observed on these surfaces (flat or microstructured) depending on the presence or absence of oligomers and their ability to diffuse out of the material. After washing samples to remove any untethered oligomeric chains, or after oxygen plasma treatment to convert the surface to a thin layer of silica, we decouple the contributions of stiffness, oligomers, and pendant chains to the stick-slip behavior. The stick phase is mainly controlled by the stiffness while the amount of untethered oligomers and pendant chains available at the contact interface defines the slip phase. A large amount of oligomers and pendant chains resulted in a large slip time, dominating the period of stick-slip motion.

Bioinspired orientation-dependent friction.

Spatular terminals on the toe pads of a gecko play an important role in directional adhesion and friction required for reversible attachment. Inspired by the toe pad design of a gecko, we study friction of polydimethylsiloxane (PDMS) micropillars terminated with asymmetric (spatular-shaped) overhangs. Friction forces in the direction of and against the spatular end were evaluated and compared to friction forces on symmetric T-shaped pillars and pillars without overhangs. The shape of friction curves and the values of friction forces on spatula-terminated pillars were orientation-dependent. Kinetic friction forces were enhanced when shearing against the spatular end, while static friction was stronger in the direction toward the spatular end. The overall friction force was higher in the direction against the spatula end. The maximum value was limited by the mechanical stability of the overhangs during shear. The aspect ratio of the pillar had a strong influence on the magnitude of the friction force, and its contribution surpassed and masked that of the spatular tip for aspect ratios of >2.

Reversible adhesion switching of porous fibrillar adhesive pads by humidity.

We report reversible adhesion switching on porous fibrillar polystyrene-block-poly(2-vinyl pyridine) (PS-b-P2VP) adhesive pads by humidity changes. Adhesion at a relative humidity of 90% was more than nine times higher than at a relative humidity of 2%. On nonporous fibrillar adhesive pads of the same material, adhesion increased only by a factor of ~3.3. The switching performance remained unchanged in at least 10 successive high/low humidity cycles. Main origin of enhanced adhesion at high humidity is the humidity-induced decrease in the elastic modulus of the polar component P2VP rather than capillary force. The presence of spongelike continuous internal pore systems with walls consisting of P2VP significantly leveraged this effect. Fibrillar adhesive pads on which adhesion is switchable by humidity changes may be used for preconcentration of airborne particulates, pollutants, and germs combined with triggered surface cleaning.

Additive Manufacturing Provides Infinite Possibilities for Self-Sensing Technology.

Integrating sensors and other functional parts in one device can enable a new generation of integrated intelligent devices that can perform self-sensing and monitoring autonomously. Applications include buildings that detect and repair damage, robots that monitor conditions and perform real-time correction and reconstruction, aircraft capable of real-time perception of the internal and external environment, and medical devices and prosthetics with a realistic sense of touch. Although integrating sensors and other functional parts into self-sensing intelligent devices has become increasingly common, additive manufacturing has only been marginally explored. This review focuses on additive manufacturing integrated design, printing equipment, and printable materials and stuctures. The importance of the material, structure, and function of integrated manufacturing are highlighted. The study summarizes current challenges to be addressed and provides suggestions for future development directions.

Touch initiated on-demand adhesion on rough surfaces.

Reversible adhesion with on-demand attachment and detachment is used by many animals for their locomotion. However, achieving robust and switchable adhesion on rough surfaces in artificial adhesives remains a significant challenge. Here, we present a snail mucus-inspired touch-initiate adhesive (TIA), showing robust adhesions on various surfaces. TIA is a polymeric hydrogel photo-cured with the presence of supersaturated sodium acetate (NaAc) in the precursor solution. TIA is soft and flexible at room temperature, allowing it to form conformal contact with objects with various surfaces. The contact with the target surface immediately initiates the crystallization of TIA, increasing the elastic modulus of TIA by an order of magnitude. The increased modulus and the interlocking with the target surfaces thus results in an adhesion strength up to 465.56 ± 84.05 kPa. TIA can be easily detached from the surface by heating to a temperature above 58 °C, showing an adhesion strength of 12.71 ± 2.73 kPa. The detached TIA, even cooled down to and kept at room temperature, is readily used for the subsequent adhesion. The study here not only provides a highly adhesive material for on-demand attachment to various surfaces, but also proposes a new design strategy to compose smart materials.